US4250117A - 4-Hydroxy-4-methyl-cyclohexen-2-one-1 - Google Patents
4-Hydroxy-4-methyl-cyclohexen-2-one-1 Download PDFInfo
- Publication number
- US4250117A US4250117A US05/932,076 US93207678A US4250117A US 4250117 A US4250117 A US 4250117A US 93207678 A US93207678 A US 93207678A US 4250117 A US4250117 A US 4250117A
- Authority
- US
- United States
- Prior art keywords
- compound
- methyl
- hydroxy
- mixture
- cyclohexen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/713—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups a keto group being part of a six-membered ring
Definitions
- This invention relates to a novel compound useful as a perfume component. More specifically, this invention relates to 4-hydroxy-4-methyl-cyclohexan-2-one-1 useful as a perfume component.
- This invention provides 4-hydroxy-4-methyl-cyclohexen-2-one-1 having the formula (I): ##STR2##
- Compound (I) 4-Hydroxy-4-methyl-cyclohexen-2-one-1 having the formula (I) above [hereinafter "Compound (I)" of this invention] neat is a substance having a phenol-like or cattle pen-like odor. However, when Compound (I) is diluted to a great extent, it imparts a fragrance organoleptically felt to be warm and giving a sweet impression. It has been found that when Compound (I) is blended with other perfume components in a perfume composition in an amount of about 2 to about 15 ppm, preferably 5 to 10 ppm, favorable results which one can readily organoleptically recognize are obtained.
- Compound (I) of this invention when Compound (I) of this invention is mixed with various synthetic essential oils such as petigrain oil, lavandine oil, lavender oil, orange oil, lemon oil, bergamot oil, peppermint oil, spearmint oil, etc., the naturalness of the odor of the blend can be markedly increased. Further, when Compound (I) is blended with other perfume components for perfumes, soaps, foods and the like, it can also impart a fragrance organoleptically felt to be warm and giving a sweet impression.
- synthetic essential oils such as petigrain oil, lavandine oil, lavender oil, orange oil, lemon oil, bergamot oil, peppermint oil, spearmint oil, etc.
- N-(p-methylphenyl)-hydroxylamine (III) can be obtained from p-nitrotoluene (II) using the nitrobenzene reduction method as described in, for example, H. Gilman, Organic Syntheses, Collective Vol. 1, 2nd Ed., pp 445-447 (1961), John Wiley & Sons, Inc., N.Y., or Y. Ogata et al, J. Am. Chem. Soc., 86, pp 3854-3858 (1964).
- the concentrate thus obtained is purified with a diethyl ether-benzene mixture on a silica gel chromatographic column to obtain pure p-toluquinol (IV) having a melting point of 76° to 78° C.
- Compound (IV) is then partially hydrogenated in ethyl alcohol with a 5% Pd/C catalyst at room temperature (e.g., about 20°-30° C.) under a hydrogen pressure of one atm. to obtain Compound (I) having a boiling point of 101.5° to 109.5° C./2 mmHg.
- step (i) above 50 g of p-tolylhydroxyl amine obtained in step (i) above was added incrementally to 1 l of a 5% sulfuric acid aqueous solution cooled to 0° C. using an ice-NaCl bath over a period of about 15 minutes while slowly stirring the mixture. After completion of the addition, the ice-NaCl bath was removed, and the mixture was slowly stirred at room temperature (i.e., about 20°-30° C.) for 12 hours. The reaction mixture was filtered, and the filtrate was extracted with 1 l of chloroform. The chloroform was distilled off from the extract to obtain 300 g of a concentrate.
- This concentrate was then chromatographed on a silica gel column, and eluted with a diethyl ether-benzene (1:1 by volume) mixture to obtain a fraction.
- the thus-obtained fraction was concentrated to obtain 15 g of p-toluquinol.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Abstract
4-Hydroxy-4-methyl-cyclohexen-2-one-1 having the formula (I): ##STR1##
Description
This invention relates to a novel compound useful as a perfume component. More specifically, this invention relates to 4-hydroxy-4-methyl-cyclohexan-2-one-1 useful as a perfume component.
This invention provides 4-hydroxy-4-methyl-cyclohexen-2-one-1 having the formula (I): ##STR2##
4-Hydroxy-4-methyl-cyclohexen-2-one-1 having the formula (I) above [hereinafter "Compound (I)" of this invention] neat is a substance having a phenol-like or cattle pen-like odor. However, when Compound (I) is diluted to a great extent, it imparts a fragrance organoleptically felt to be warm and giving a sweet impression. It has been found that when Compound (I) is blended with other perfume components in a perfume composition in an amount of about 2 to about 15 ppm, preferably 5 to 10 ppm, favorable results which one can readily organoleptically recognize are obtained. For example, when Compound (I) of this invention is mixed with various synthetic essential oils such as petigrain oil, lavandine oil, lavender oil, orange oil, lemon oil, bergamot oil, peppermint oil, spearmint oil, etc., the naturalness of the odor of the blend can be markedly increased. Further, when Compound (I) is blended with other perfume components for perfumes, soaps, foods and the like, it can also impart a fragrance organoleptically felt to be warm and giving a sweet impression.
Compound (I) of this invention can be, for example, prepared in accordance with the following reaction schematic: ##STR3##
In the above-described reaction schematic, N-(p-methylphenyl)-hydroxylamine (III) can be obtained from p-nitrotoluene (II) using the nitrobenzene reduction method as described in, for example, H. Gilman, Organic Syntheses, Collective Vol. 1, 2nd Ed., pp 445-447 (1961), John Wiley & Sons, Inc., N.Y., or Y. Ogata et al, J. Am. Chem. Soc., 86, pp 3854-3858 (1964). More specifically, for example, 1 mole of p-nitrotoluene (II) is reduced with 2 moles of zinc dust in a solution of 1 mole of ammonium chloride, and the resulting product is recrystallized from a benzene-petroleum ether mixture to obtain Compound (III) having a melting point of 94° C. Subsequently, Compound (III) is treated with a 5% sulfuric acid aqueous solution while cooling to approximately 0° C., e.g., in accordance with the method described in S. Goodwin et al, J. Am. Chem. Soc., 79, pp 179-185 (1957). After extracting the resulting product with chloroform, the concentrate thus obtained is purified with a diethyl ether-benzene mixture on a silica gel chromatographic column to obtain pure p-toluquinol (IV) having a melting point of 76° to 78° C. Compound (IV) is then partially hydrogenated in ethyl alcohol with a 5% Pd/C catalyst at room temperature (e.g., about 20°-30° C.) under a hydrogen pressure of one atm. to obtain Compound (I) having a boiling point of 101.5° to 109.5° C./2 mmHg.
This invention is explained in more detail with reference to the following examples. Unless otherwise indicated herein, all parts, percents, ratios and the like are by weight.
The following Formulation Examples are given to illustrate representative examples of perfumes in which Compound (I) of this invention can be used. These Formulation Examples should not be construed as limiting the use of Compound (I) of this invention, however.
0.01 g (10 ppm) of Compound (I) of this invention was added to 1000 g of synthetic lavandine oil having the formulation shown in Table 1 below.
TABLE 1
______________________________________
(Formulation of Synthetic Lavandine Oil)
Weight
Components (g)
______________________________________
Cineole 200
Ocimene 100
Camphor 90
Aldehyde C.sub.13 90
(5,2,1,0)Tricyclo-3-decen-8-yl Acetate
70
Bornyl Acetate 50
iso-Pulegyl Acetate 50
Borneol 42
iso-Dihydro-lavandulyl Aldehyde
42
Octyl iso-Butyrate 40
Ethyl Amyl Ketone 30
Heptyl Aldehyde* 28
Hexyl Aldehyde* 14
Octyl Aldehyde* 14
Cuminaldehyde* 14
Linalyl iso-Valerate 28
Linalyl iso-Butyrate 8
Linalool Oxide 8
n-Octyl Alcohol 14
n-Hexyl Alcohol 8
n-Octyl Acetate 8
n-Hexyl Acetate 14
Dihydro Terpineol 14
Geraniol 8
n-Amyl Alcohol 6
Methyl Chrysanthemate 10
Total: 1000
______________________________________
*1% in benzyl benzoate.
As a result of an organoleptic evaluation using 10 panelists, all of the 10 panelists recognized that the naturalness of the resulting perfume composition was markedly improved as compared with the same perfume composition to which Compound (I) of this invention was not added.
0.005 g (5 ppm) of Compound (I) of this invention was added to 1000 g of synthetic peppermint oil having the formulation shown in Table 2 below.
TABLE 2
______________________________________
(Formulation of Synthetic Peppermint Oil)
Weight
Components (g)
______________________________________
Menthol 474
Menthone 250
1,8-Cineole 65
Menthyl Acetate 36
iso-Menthone 35
Terpinene-4-ol 32
α-Terpineol 20
Menthofuran 17
l-Limonene 15
β-Pinene 12
α-Pinene 9
Piperitone 5
Caryophyllene 5
Linalool 4
3-Octanol 3
p-Cymene 3
β-Myrcene 3
1-Octen-3-ol 2
iso-Valeraldehyde 2
cis-Jasmone 2
iso-Amyl Alcohol 0.6
cis-3-Hexenol 0.5
Mint Lactone 0.5
1-Octen-3-yl Isovalerate
0.4
n-Hexyl Aldehyde 0.4
t-2-Hexenol 0.4
Eugenol 0.4
n-Hexanol 0.3
t-Jasmone 0.3
3-Octyl Acetate 0.3
1-Octen-3-yl Acetate
0.3
Pulegone 0.3
iso-Valeric Acid 0.3
cis-3-Hexenyl Acetate
0.2
Citronellyl Acetate 0.2
Geranyl Acetone 0.2
Carbacrol 0.2
2-Methylpropanol 0.1
Thymol 0.1
Total: 1000
______________________________________
As a result of an organoleptic evaluation using 10 panelists, all of the 10 panelists recognized that the naturalness of the resulting perfume composition was markedly improved as compared with the same perfume composition to which Compound (I) of this invention was not added.
281 g (2.05 moles) of p-nitrotoluene, 125 g (2.35 moles) of ammonium chloride and 4 l of water were charged into a 10-l reaction flask. 310 g (4.74 moles) of zinc dust was added thereto at room temperature (i.e., about 20°-30° C.) over a period of 15 minutes while stirring the mixture, and the mixture was stirred for an additional 30 minutes. In this case, the temperature of the reaction system increased to 65° to 70° C. with stirring. Thereafter, the reaction mixture was filtered, and the filtrate was saturated with sodium chloride. The filtrate was allowed to stand in a cool place for 24 hours. The precipitated crystals were filtered, and recrystallized from 1 l of a benzene-petroleum ether (1:1 by volume) mixture to obtain 50 g of p-tolylhydroxyl amine.
50 g of p-tolylhydroxyl amine obtained in step (i) above was added incrementally to 1 l of a 5% sulfuric acid aqueous solution cooled to 0° C. using an ice-NaCl bath over a period of about 15 minutes while slowly stirring the mixture. After completion of the addition, the ice-NaCl bath was removed, and the mixture was slowly stirred at room temperature (i.e., about 20°-30° C.) for 12 hours. The reaction mixture was filtered, and the filtrate was extracted with 1 l of chloroform. The chloroform was distilled off from the extract to obtain 300 g of a concentrate. This concentrate was then chromatographed on a silica gel column, and eluted with a diethyl ether-benzene (1:1 by volume) mixture to obtain a fraction. The thus-obtained fraction was concentrated to obtain 15 g of p-toluquinol.
50 g of p-toluquinol obtained in step (ii) above was dissolved in 50 g of ethyl alcohol. The mixture was hydrogenated with 5% palladium-on-carbon as a catalyst while shaking the mixture at room temperature under a hydrogen pressure of one atm. When 80% of the amount of hydrogen theoretically necessary for hydrogenation to an extent of 0.5 mole was absorbed, the reaction was stopped. After filtering off the catalyst, the residue was distilled under reduced pressure to obtain 47 g of a fraction having a boiling point of 101.5°-109.5° C./2 mmHg. This fraction was a colorless liquid and had the following characteristics.
______________________________________
Specific Gravity d.sub.20.sup.20 :
1.0842
Refractive Index n.sub.D.sup.20 :
1.5163
Mass Spectral Analysis:
M.sup.⊕ 126 111 (M--CH.sub.3)
Infrared Analysis:
ν cm.sup.-1 3400 (--OH), 1675 (C═O)
Nuclear Magnetic Resonance Analysis:
δ ppm
1.4 (3H, s) H.sub.7
1.9-2.7 (4H, m) H.sub.5, H.sub.6
3.3 (1H, m) OH
5.8 (1H, d) H.sub.3
6.7 (1H, d) H.sub.2
______________________________________
The above results confirm that Compound (I) of this invention had the following formula: ##STR4##
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (1)
1. 4-Hydroxy-4-methyl-cyclohexen-2-one-1 having the formula (I): ##STR5##
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52094162A JPS591249B2 (en) | 1977-08-08 | 1977-08-08 | 4-Hydroxy-4-methyl-cyclohexen-2-one-1 |
| JP52-94162 | 1977-08-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4250117A true US4250117A (en) | 1981-02-10 |
Family
ID=14102665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/932,076 Expired - Lifetime US4250117A (en) | 1977-08-08 | 1978-08-08 | 4-Hydroxy-4-methyl-cyclohexen-2-one-1 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4250117A (en) |
| JP (1) | JPS591249B2 (en) |
| CH (1) | CH634812A5 (en) |
| DE (1) | DE2834500C2 (en) |
| FR (1) | FR2399996A1 (en) |
| GB (1) | GB2002373B (en) |
| IT (1) | IT1156895B (en) |
| NL (1) | NL180205C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429164A (en) | 1981-02-25 | 1984-01-31 | Otsuka Kagaku Yakuhin Kabushini Kaisha | Cyclohexadiene derivatives and process for preparing the same |
| US4871877A (en) * | 1988-05-20 | 1989-10-03 | Ethyl Corporation | Gem-disubstituted cyclohexadienones and their production |
| US20060002876A1 (en) * | 2004-07-02 | 2006-01-05 | Cahen Christine M | Personal care compositions with improved hyposensitivity |
| US9006169B2 (en) | 2005-06-03 | 2015-04-14 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957887A (en) * | 1972-09-18 | 1976-05-18 | Teijin Limited | Process for preparing trimethylhydroquinone |
| US4010205A (en) * | 1973-12-07 | 1977-03-01 | Firmenich S.A. | Process for the preparation of a diketone derivative |
| US4076854A (en) * | 1977-03-03 | 1978-02-28 | International Flavors & Fragrances Inc. | Flavoring with a cyclohexadiene derivative |
| US4084009A (en) * | 1977-03-03 | 1978-04-11 | International Flavors & Fragrances Inc. | Flavoring with a hydroxy cyclohexenone derivative |
-
1977
- 1977-08-08 JP JP52094162A patent/JPS591249B2/en not_active Expired
-
1978
- 1978-08-03 GB GB7832076A patent/GB2002373B/en not_active Expired
- 1978-08-07 DE DE2834500A patent/DE2834500C2/en not_active Expired
- 1978-08-07 NL NLAANVRAGE7808253,A patent/NL180205C/en not_active IP Right Cessation
- 1978-08-07 IT IT50633/78A patent/IT1156895B/en active
- 1978-08-08 US US05/932,076 patent/US4250117A/en not_active Expired - Lifetime
- 1978-08-08 FR FR7823381A patent/FR2399996A1/en active Granted
- 1978-08-08 CH CH841478A patent/CH634812A5/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957887A (en) * | 1972-09-18 | 1976-05-18 | Teijin Limited | Process for preparing trimethylhydroquinone |
| US4010205A (en) * | 1973-12-07 | 1977-03-01 | Firmenich S.A. | Process for the preparation of a diketone derivative |
| US4076854A (en) * | 1977-03-03 | 1978-02-28 | International Flavors & Fragrances Inc. | Flavoring with a cyclohexadiene derivative |
| US4084009A (en) * | 1977-03-03 | 1978-04-11 | International Flavors & Fragrances Inc. | Flavoring with a hydroxy cyclohexenone derivative |
Non-Patent Citations (1)
| Title |
|---|
| Gaoni, "Tetrahedron," vol. 28, pp. 5525-5531, (1972), Pergamon Press. * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429164A (en) | 1981-02-25 | 1984-01-31 | Otsuka Kagaku Yakuhin Kabushini Kaisha | Cyclohexadiene derivatives and process for preparing the same |
| US4871877A (en) * | 1988-05-20 | 1989-10-03 | Ethyl Corporation | Gem-disubstituted cyclohexadienones and their production |
| US20060002876A1 (en) * | 2004-07-02 | 2006-01-05 | Cahen Christine M | Personal care compositions with improved hyposensitivity |
| WO2006014447A1 (en) * | 2004-07-02 | 2006-02-09 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
| EP1666021A1 (en) * | 2004-07-02 | 2006-06-07 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
| JP2008505188A (en) * | 2004-07-02 | 2008-02-21 | ザ プロクター アンド ギャンブル カンパニー | Personal care composition with reduced irritation |
| AU2005269998B2 (en) * | 2004-07-02 | 2009-01-08 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
| US8455417B2 (en) | 2004-07-02 | 2013-06-04 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
| US10183051B2 (en) | 2004-07-02 | 2019-01-22 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
| US9006169B2 (en) | 2005-06-03 | 2015-04-14 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
| US9585866B2 (en) | 2005-06-03 | 2017-03-07 | The Procter & Gamble Company | Personal care compositions with improved hyposensitivity |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2399996B1 (en) | 1980-07-18 |
| CH634812A5 (en) | 1983-02-28 |
| FR2399996A1 (en) | 1979-03-09 |
| NL7808253A (en) | 1979-02-12 |
| GB2002373A (en) | 1979-02-21 |
| DE2834500C2 (en) | 1982-12-30 |
| IT1156895B (en) | 1987-02-04 |
| DE2834500A1 (en) | 1979-02-22 |
| JPS5430135A (en) | 1979-03-06 |
| GB2002373B (en) | 1982-01-20 |
| NL180205C (en) | 1987-01-16 |
| IT7850633A0 (en) | 1978-08-07 |
| NL180205B (en) | 1986-08-18 |
| JPS591249B2 (en) | 1984-01-11 |
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